Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries
Abstract
Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange current density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li2S8 andmore »
- Authors:
-
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- California State Univ. (CalState), Northridge, CA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- 24M Technologies, Cambridge, MA (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Materials Sciences and Engineering Division; Joint Center for Energy Storage Research (JCESR)
- OSTI Identifier:
- 1348933
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Volume: 163; Journal Issue: 14; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 36 MATERIALS SCIENCE
Citation Formats
Fan, Frank Y., Pan, Menghsuan Sam, Lau, Kah Chun, Assary, Rajeev S., Woodford, William H., Curtiss, Larry A., Carter, W. Craig, and Chiang, Yet -Ming. Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries. United States: N. p., 2016.
Web. doi:10.1149/2.1181614jes.
Fan, Frank Y., Pan, Menghsuan Sam, Lau, Kah Chun, Assary, Rajeev S., Woodford, William H., Curtiss, Larry A., Carter, W. Craig, & Chiang, Yet -Ming. Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries. United States. https://doi.org/10.1149/2.1181614jes
Fan, Frank Y., Pan, Menghsuan Sam, Lau, Kah Chun, Assary, Rajeev S., Woodford, William H., Curtiss, Larry A., Carter, W. Craig, and Chiang, Yet -Ming. Fri .
"Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries". United States. https://doi.org/10.1149/2.1181614jes. https://www.osti.gov/servlets/purl/1348933.
@article{osti_1348933,
title = {Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries},
author = {Fan, Frank Y. and Pan, Menghsuan Sam and Lau, Kah Chun and Assary, Rajeev S. and Woodford, William H. and Curtiss, Larry A. and Carter, W. Craig and Chiang, Yet -Ming},
abstractNote = {Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange current density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li2S8 and Li2S4).},
doi = {10.1149/2.1181614jes},
journal = {Journal of the Electrochemical Society},
number = 14,
volume = 163,
place = {United States},
year = {Fri Nov 25 00:00:00 EST 2016},
month = {Fri Nov 25 00:00:00 EST 2016}
}
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Works referenced in this record:
Morphological and Structural Studies of Composite Sulfur Electrodes upon Cycling by HRTEM, AFM and Raman Spectroscopy
journal, January 2010
- Elazari, Ran; Salitra, Gregory; Talyosef, Yossi
- Journal of The Electrochemical Society, Vol. 157, Issue 10
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Electrochemistry of a nonaqueous lithium/sulfur cell
journal, January 1983
- Yamin, H.; Peled, E.
- Journal of Power Sources, Vol. 9, Issue 3
Critical Link between Materials Chemistry and Cell-Level Design for High Energy Density and Low Cost Lithium-Sulfur Transportation Battery
journal, January 2015
- Eroglu, Damla; Zavadil, Kevin R.; Gallagher, Kevin G.
- Journal of The Electrochemical Society, Vol. 162, Issue 6
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Mechanism and Kinetics of Li 2 S Precipitation in Lithium-Sulfur Batteries
journal, August 2015
- Fan, Frank Y.; Carter, W. Craig; Chiang, Yet-Ming
- Advanced Materials, Vol. 27, Issue 35
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
A review of blended cathode materials for use in Li-ion batteries
journal, February 2014
- Chikkannanavar, Satishkumar B.; Bernardi, Dawn M.; Liu, Lingyun
- Journal of Power Sources, Vol. 248
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
New insights into the limiting parameters of the Li/S rechargeable cell
journal, February 2012
- Barchasz, Céline; Leprêtre, Jean-Claude; Alloin, Fannie
- Journal of Power Sources, Vol. 199, p. 322-330
Challenges and Prospects of Lithium–Sulfur Batteries
journal, June 2012
- Manthiram, Arumugam; Fu, Yongzhu; Su, Yu-Sheng
- Accounts of Chemical Research, Vol. 46, Issue 5
Mechanistic modeling of polysulfide shuttle and capacity loss in lithium–sulfur batteries
journal, August 2014
- Hofmann, Andreas F.; Fronczek, David N.; Bessler, Wolfgang G.
- Journal of Power Sources, Vol. 259
A zero dimensional model of lithium–sulfur batteries during charge and discharge
journal, January 2016
- Marinescu, Monica; Zhang, Teng; Offer, Gregory J.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 1
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Rechargeable Lithium Sulfur Battery
journal, May 2003
- Cheon, Sang-Eun; Ko, Ki-Seok; Cho, Ji-Hoon
- Journal of The Electrochemical Society, Vol. 150, Issue 6, p. A800-A805
Insight into lithium–sulfur batteries: Elementary kinetic modeling and impedance simulation
journal, December 2013
- Fronczek, David N.; Bessler, Wolfgang G.
- Journal of Power Sources, Vol. 244
Glassy carbon electrodes
journal, July 2001
- Dekanski, Aleksandar; Stevanović, Jasna; Stevanović, Rade
- Carbon, Vol. 39, Issue 8
Polysulfide Flow Batteries Enabled by Percolating Nanoscale Conductor Networks
journal, March 2014
- Fan, Frank Y.; Woodford, William H.; Li, Zheng
- Nano Letters, Vol. 14, Issue 4, p. 2210-2218
Li–O2 and Li–S batteries with high energy storage
journal, January 2012
- Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
- Nature Materials, Vol. 11, Issue 1, p. 19-29
A membrane-free lithium/polysulfide semi-liquid battery for large-scale energy storage
journal, January 2013
- Yang, Yuan; Zheng, Guangyuan; Cui, Yi
- Energy & Environmental Science, Vol. 6, Issue 5
Amphiphilic Surface Modification of Hollow Carbon Nanofibers for Improved Cycle Life of Lithium Sulfur Batteries
journal, February 2013
- Zheng, Guangyuan; Zhang, Qianfan; Cha, Judy J.
- Nano Letters, Vol. 13, Issue 3, p. 1265-1270
Activation and deactivation of glassy carbon electrodes
journal, June 1985
- Hu, Ing-Feng; Karweik, Dale H.; Kuwana, Theodore
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 188, Issue 1-2
Wall Slip Corrections for Couette and Parallel Disk Viscometers
journal, January 1988
- Yoshimura, Ann; Prud'homme, Robert K.
- Journal of Rheology, Vol. 32, Issue 1
Charge Transfer and Transport Properties of Lithium Polysfulfide Solutions
journal, June 2014
- Woodford, William; Fan, Frank; Baram, Nir
- ECS Meeting Abstracts, Vol. MA2014-04, Issue 3
Works referencing / citing this record:
Toward Better Lithium–Sulfur Batteries: Functional Non-aqueous Liquid Electrolytes
journal, August 2018
- Xiong, Shizhao; Regula, Michael; Wang, Donghai
- Electrochemical Energy Reviews, Vol. 1, Issue 3
Revisiting the Role of Polysulfides in Lithium-Sulfur Batteries
journal, March 2018
- Li, Gaoran; Wang, Shun; Zhang, Yining
- Advanced Materials, Vol. 30, Issue 22
Rational Design of Nanostructured Functional Interlayer/Separator for Advanced Li-S Batteries
journal, February 2018
- Jeong, Yo Chan; Kim, Jae Ho; Nam, Seunghoon
- Advanced Functional Materials, Vol. 28, Issue 38
Cell Concepts of Metal–Sulfur Batteries (Metal = Li, Na, K, Mg): Strategies for Using Sulfur in Energy Storage Applications
journal, September 2017
- Medenbach, Lukas; Adelhelm, Philipp
- Topics in Current Chemistry, Vol. 375, Issue 5
Current Status and Future Prospects of Metal–Sulfur Batteries
journal, May 2019
- Chung, Sheng‐Heng; Manthiram, Arumugam
- Advanced Materials, Vol. 31, Issue 27
A Bifunctional Perovskite Promoter for Polysulfide Regulation toward Stable Lithium-Sulfur Batteries
journal, November 2017
- Kong, Long; Chen, Xiang; Li, Bo-Quan
- Advanced Materials, Vol. 30, Issue 2
Mesoscale Physicochemical Interactions in Lithium–Sulfur Batteries: Progress and Perspective
journal, October 2017
- Liu, Zhixiao; Mistry, Aashutosh; Mukherjee, Partha P.
- Journal of Electrochemical Energy Conversion and Storage, Vol. 15, Issue 1
Intercalation-conversion hybrid cathodes enabling Li–S full-cell architectures with jointly superior gravimetric and volumetric energy densities
journal, March 2019
- Xue, Weijiang; Shi, Zhe; Suo, Liumin
- Nature Energy, Vol. 4, Issue 5
Factors of Kinetics Processes in Lithium–Sulfur Reactions
journal, December 2019
- Tang, Xiaonan; Xu, Zichen; Sun, Zhenhua
- Energy Technology, Vol. 7, Issue 12
Revisiting the positive roles of liquid polysulfides in alkali metal–sulfur electrochemistry: from electrolyte additives to active catholyte
journal, January 2019
- Chang, Caiyun; Pu, Xiong
- Nanoscale, Vol. 11, Issue 45
Electrodeposition Kinetics in Li-S Batteries: Effects of Low Electrolyte/Sulfur Ratios and Deposition Surface Composition
journal, January 2017
- Fan, Frank Y.; Chiang, Yet-Ming
- Journal of The Electrochemical Society, Vol. 164, Issue 4
Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries
journal, January 2018
- Tsai, Ping-Chun; Wen, Bohua; Wolfman, Mark
- Energy & Environmental Science, Vol. 11, Issue 4
A Toolbox for Lithium-Sulfur Battery Research: Methods and Protocols
journal, June 2017
- Zhang, Ge; Zhang, Ze-Wen; Peng, Hong-Jie
- Small Methods, Vol. 1, Issue 7
Factors of Kinetics Processes in Lithium–Sulfur Reactions
journal, May 2019
- Tang, Xiaonan; Xu, Zichen; Sun, Zhenhua
- Energy Technology, Vol. 7, Issue 12
Structural and Transport Properties of Li/S Battery Electrolytes: Role of the Polysulfide Species
journal, April 2019
- Park, Chanbum; Ronneburg, Arne; Risse, Sebastian
- The Journal of Physical Chemistry C, Vol. 123, Issue 16